Production of plastic masses



Fetented @ct. 25, 1932 UNITED STATES aasaoza PATENT OFFICE m'rm LUTHER, or Hamill, mm ROBERT HELD, or orrau, Guam, assrenons r0 I. o. rmmrmnusram axrrmrensnnnscnarr, or rnanxroar-orr-rnn-mm, enmmmr, A oonrom'rron or Gunman PBODUGIION OI PLASTIC MASSES Drawing. Application filed June 3, 1929, Serial No. 868,185, and in Germany June 18, 1988.

The present invention relates to the production of plastic masses.

It is alread known that by the oxidation )f paraflin hy rocarbons, waxes such as paraffin waxes and the like, for example by passing a strong current of air throu h the initial material in the liquid state pre erably while heating and in the presence of fillers possess ing a large superficial area, a mixture of organic products containing oxygen is obtained, which consists mainly of neutral oxy en compounds, saturated fatty acids and ark colnred acid products, insoluble in petroleum ether. The acids which are insoluble in petroleum ether ma be separated from the saturated fatty acids 'for example by pressing or sweating or a combination of both these processes.

We have now found that valuable plastic products are obtained by heating that liquid part of the acids obtained by t e oxidation of paraflin hydrocarbons, waxes such as parafiin waxes and the like, which is insoluble in petroleum ether with aliphatic compounds which contain two or more hydroxyl groups in the molecule to a temperature above about 0., if desired with the addition ofother substances. Usually heating to a temperature between 150 and 220 C. is suflicient and the reaction proceeds in most cases quickly enou h for technical purposes when heating to a out C. The quantity employed of the hydroxyl bearin organic compounds should correspond to a out one half of that corresponding to the saponifieation value acid component, buta'higher quantity may also be employed. According to the method of production these plastic products possess the properties of linoxyn or rubber oil substitute and are well adapted for employment forexample in the manufacture of linoleum or for filling or improving rubber products,

lacquers, artificial masses and the like. The

following may he mentioned among others as suitable organic compounds containing hydroxyl groups:-glycols, ethers of glycols with the same or other glycols, glycerdl, mannitol, sorbitol, glucose and the like.

The treament may be carried out in any Moran and suitable apparatus if desired in the presence of catalysts splitting oil water,

and at normal, increased or reduced pressures. Suitable substances to be added are for example metal compounds, as for exam le lead oxide and the like, which with the said acids give agents of siccative action, or also a sulphurizing substance such as sulphur or compounds containing sulphur and the like. The said acids may also be heated in admixture with unsaturated acids for example linoleic acid or with hydroxy carboxylic acids, such as ricinoleic acid, which are equivalents to the unsaturated acids inasmuch as they are capable of forming unsaturated acids by splitting off water, or glycerides of the said acids. The process in accordance with the present invention may also be advantageously carried out by treating the acids or mixtures of acids with siccatives, i. e. compounds of theheavy metals, such as compounds of lead, manganese or cobalt or several of such compounds, or with sulphur previously to the esterification. In the treatment it is not necessary tc employ the stoichiometrical quantity of hydroxyl compounds corresponding to an'esterification of the organic acids present, but valuable plastic products are obtained by employing considerably smaller quantities, for example half of the theoretically calculated quantlty. It is advantageous to carry out the heat treatment at an elevated temperature in the liq uid phase while passing throu h a gas or vapour such asnitrogen or carbon dioxide. In any case the process according to the present invention apparently leads to an esterification of acid constituents contained in the fraction of the oxidation products insoluble in petroleum ether with the hydroxyl-bearing compounds and a simultaneous polymerization of the acids and of the ester formed.

The following exampleswill further illustrate the nature of the invention but the invention is not restricted to these examples. as

The parts are by weight.

Example 1 ing the crude oxidation product, which is insoluble in petroleum ether' and has a saponification value of 235, are heated together with 19.3 parts of glycerol at from 170 to 210 centigrade in vacuo while stirring for an hour. After a further half an hour the mixture becomes viscous and finally solid. The reaction product is a dark, tenacious, non-greasy, very elastic mass which is insoluble in alcohol, petroleum ether and acetone, soluble with difficulty higher alcohols and ethers, and soluble in benzene, pyridine, trichlorethylene, and hot glacial acetic acid. It can be saponified with lyes.

Example 2 The substances described in Example 1 are mixed together-in the same quantities with an addition of 10 per cent of sulphur calculated with reference to the weight of acid employed. Aft-er heating this mixture at from 150 to 170 centigrade for 4 hours in vacuo while stirring, a deep black, crumbly mass which in other properties is similar to that described in Example 1 is obtained.

Example 3 150 parts of liquid acid product insoluble in petroleum ether and having a saponification "alue of 258, obtained from an oxidation product of paraflin wax, are heated together with 2 per cent of lead oxide in vacuo at 160 centigrade while stirring for 2 hours, and then after adding the calculated quantity of glycerol heated for a further 2% hours at from 200 to 210 centigrade. A product having similar properties to those described in Example 1, but which has greater density and tenacity, is obtained.

Example 4 The substances described in Example 1 are mixed in thequantities there given with an addition of 20 parts of linseed oil. After heating for '3 hours at from 210 to 240 Centigrade a dark mass having similar properties to the product in Example 1, but being a little more tenacious, is obtained.

Example 5 compound containing at least two hydroxyl groups in its molecule to a temperature above about 150 C.

i 2. The process for the production of plas tic masses which com rises heating the li uid acid portion, insolu le in petroleum et er of a roduct of the destructive oxidation 0% para hydrocarbons, with an unsaturated organic acid and an aliphatic compound containing at least two hydroxyl groups in its mglecule, to a temperature above about 150 3. The process for the production of plastic masses which comprises heating the liquid acid portion, insoluble in troleum ether, of a product of the destructive oxidation of paraflin hydrocarbons, with a polyh dric'aliphatic alcohol, to a temperature a ove about 150 C. in the presence of a siccative.

4. The process for the production of plastic masses which comprises heating the li uid acid portion, insoluble in petroleum et er,

of a product of the destruction oxidation of paraflin hydrocarbons, with an unsaturated aliphatic acid and an organic compound containing at least two hydroxyl groups in its molecule, to a temperature above about 150 C. and in the presence of a siccative.

5. Plastic, tenacious masses comprising a heat reaction product of the liquid acid portion, insoluble in petroleum ether, of a prodduct of the destructive oxidation of parafiin hydrocarbons, with an aliphatic compound containing at least two hydroxyl groups in its molecule. y

6. Plastic, tenacious masses comprising a heat reaction product of the liquid acid portion, insoluble in petroleum ether, of a product of the destructive oxidation of paraflin hydrocarbons, and an aliphatic compound containing at least two hydroxyl groups in its molecule, said reaction product being produced in the presence of a siccative.

The process for the production of plastic masses which comprises heating at a temperature ranging from about 150 to about 240 C. the liquid acid portion, insoluble in petroleum ether, of a product of the destructive oxidation of paraffin hydrocarbons, with an aliphatic compound containing at least two hydroxyl groups in its molecule.

8. The process for the-production of plastic masses which comprises heating at a temperature ran 'ng from about 150 to about 240 C. the liquid acid portion, insoluble in petroleum ether, of a product of the destructive oxidation of paraflin wax, with an ali-' phatic compound containing at least two hydroxyl groups in its molecule.

9. The process for the production of plastic masses which comprises heating at a temperature ranging from about 150 to about 240 C. the liquid acid portion, insoluble in petroleum ether, having a saponification Value ranging from about 235 to about 258 of rseeeae a roduct of the destructive oxidation of paran hydrocarbons, with an aliphatic compound containing at least two hydroxyl groups in its molecule,

10. The process for the production of plus-- tic messes which comprises heating at e temperature rangin from about 150 to about 240 C. the liquld acid portion, insoluble in petroleum ether, having a saponification value ranging from about 235 to about 258,

of a product of the destructive oxidation of para n wax with an aliphatic compound containing at least two hydroxyl groups in its molecule.

11. The process for the production of plastic masses which comprises heating at a temperature ranging from about 150 to about 240 C. the liquid acid portion, insoluble in petroleum ether of a product of the destructive oxidation of parafin hydrocarbons, with glycerol,

12. The process for the production of plastic masses which comprises heating at a tenn perature ranging from about 150 to about 240 C. the liquid 'ecid portion, insoluble in petroleum ether, having a saponification value ranging from about 235 to about 258, of a, roduct of the destructive oxidation oi para wax with glycerol.

13. The process for the'production of plies tic masses which comprises heating at e tem perature ranging from about 150 to about 240 C. the liquid acid portion, insoluble in petroleum ether, heving a saponification value ranging from about 235 to about 258 of a roduct of the distructive oxidation 0% para 11 wax with of a siccative.

14:. Plastic, tenacious masses comprisin a heat reaction product of the li uid aci portion, insoluble in petroleum e er, of 21 glycerol in the resence product of the destructive oxidation or? pareihn wax, having a saponification value ranging1 from about 235 to about 258, with glycero our hands.

MARTIN LUTHER. ROBERT HELD.

15. Plastic, tenacious masses comprising 

